The present invention relates to novel copolymers and to their use as additives in drilling fluids, for cementation, as completion and workover fluids, and for water shutoff.
In deep underground wells for recovering oil and natural gas deposits, the use of drilling fluids and cement slurries has been known for some considerable time. The functions of drilling fluids are to carry the drilled rock fragments and the so-called drill dust, to lubricate the bit and the drill pipe, to seal porous rock strata, and to compensate the reservoir pressure by hydrostatic pressure. For the latter purpose, drilling fluids are required to have a high specific weight. This is achieved by adding preferably barite, salts, or clays. Further important features of drilling fluids are temperature stability and appropriate flow properties that are not greatly influenced by changes in electrolyte concentration. The commonest additives for controlling the viscosity and water loss of drilling fluids are polymers such as starch and starch ethers such as carboxymethyl starch, carboxymethylcellulose and carboxymethylhydroxyethylcellulose. However, these additives become ineffective at temperatures above about 120xc2x0 C. (starch and derivatives) or 140-150xc2x0 C. (carboxymethylcellulose and carboxymethylhydroxyethylcellulose). Since the 1950s, copolymers of the acrylamide-acrylate type, which are stable even at temperatures of more than 200xc2x0 C., have been used predominantly in salt-free drilling fluids. The 1970s saw the development of salt-stable copolymers with monomers containing sulfo groups and stable at more than 200xc2x0 C. (U.S. Pat. Nos. 3,629,101, 4,048,077, 4,309,523).
Cement slurries and completion fluids are used in addition as borehole fluids in the case of deep underground drilling for oil or natural gas. When the borehole has reached a certain depth, iron pipes, known as casing pipes, are introduced into the borehole, the bit for drilling out the next rock strata down being passed through the space inside the pipes. For this purpose, the casing pipes must be secured, i.e., a cement slurry which sets to form a solid stonelike mass must be pumped into the cavity between the rock formation and the outer casing walls, known as the annular space. The hardened cement which forms must be impermeable to gases and liquids in order that no gas and/or oil can flow out of the carrier formation into other formations or as far as the surface. Stringent requirements are placed on the cement slurry to be pumped. It should be readily pumpable, i.e., of extremely low viscosity, and yet should not separate out. The release of water by the cement slurry to the porous rock formation should be low in order to prevent the formation of thick filter cakes at the borehole wall; thick filter cakes would increase the pumping pressure to such an extent, owing to the constriction of the annular space, that the porous rock formation would disintegrate. In addition, if the release of water were excessive, the cement slurry would not set fully and would become permeable to gas and oil. On the other hand, the jacket of cement which forms in the annular space must attain a certain strength as rapidly as possible, and setting must not be accompanied by any shrinkage as this would result in flow channels for gas, oil and water. Establishing the properties of the cement slurry at an optimum is possible only by means of additives.
The most important additives for regulating the setting process are retardants, accelerators, dispersants for liquefaction, and water loss reducers. In some cases, these additives have more than one function. Dispersants such as lignosulfonates and polymethylenenapthalenesulfonates retard setting and also bring about a certain reduction in water loss. Some water loss reducers retard setting and greatly increase viscosity.
Effective water loss reducers used in practice for cement and gypsum slurries include a very wide variety of polymers, copolymers, and combinations thereof.
EP-A-0 483 638 discloses copolymers of acrylamidopropenylmethylenesulfonic acid (AMPS), open-chain and cyclic N-vinylamides, and diolefinically unsaturated ammonium compounds. These monomer combinations produce copolymers which in certain cases are crosslinked and whose thermal stability is inadequate for certain applications.
WO-83/02449 discloses copolymers of acrylic sulfonates such as AMPS, for example, open-chain or cyclic N-vinylamides, amides of acrylic or methacrylic acid, vinylimidazolyl compounds and olefinically unsaturated compounds carrying hydroxyl or alkoxy radicals. The copolymer is crosslinked by using from 5 to 25% by weight of diolefinically unsaturated compounds as further monomers.
DE-A-31 44 770 discloses copolymers of acrylamide or methacrylamide, styrenesulfonates, and N-vinylamides. The latter can be cyclic or open-chain, although the simultaneous use of cyclic and open-chain N-vinylamides is not disclosed.
EP-A-0 141 327 discloses copolymers of (meth)acrylic acid or derivatives thereof, acrylic sulfonates such as, for example, AMPS and N-vinylamides. Here again, the N-vinylamides can be cyclic or open-chain, but not both in the same polymer.
The multiplicity of compounds developed makes it clear that it is always difficult to formulate an optimum cement slurry. In the case of individual parameters predetermined by the type of cementation, the necessary properties must be established at acceptable levels using additives. The large number of compounds developed for reducing water loss indicates just how much of a problem it generally is to establish a required level of water release without substantially increasing the viscosity, to establish the setting time in accordance with the requirement, and to minimize sedimentation. The prior art water-loss-reducing polymers more or less greatly increase the viscosity of the cement slurries, which are usually of high density. In order to be readily pumpable, however, the viscosity of the cement slurries must be kept low. A pumping rate which permits turbulent flow should be possible. Only under such conditions is the drilling fluid completely displaced. This is a prerequisite of effective cementation. In the case of inclined boreholes, the fluid can only be displaced effectively by means of a strong turbulent flow.
High density salt solutions which compensate the reservoir pressure are used for the completion of oil and natural gas wells. The infiltration of such solutions into the reservoir must be kept to a minimum. However, hydroxyethylcelluloses are unsuitable for the prevailing temperatures, which extend to above 200xc2x0 C., and the high salinities and densities due to CaCl2 and CaBr2.
In the light of the prior art, the object of the present invention was to discover copolymers which are suitable for use in drilling fluids which can in turn be used in an extended temperature range relative to the prior art. The copolymers of the invention should no longer have the thermal instability known from the prior art. A further object was that the copolymers should represent an improvement over the prior art by exhibiting a more uniform flow behavior of the drilling fluid following its preparation and after exposure (aging) within the temperature range in question of from about 130xc2x0 C. to more than 200xc2x0 C. The present invention should therefore solve the problem encountered in the prior art of the nonuniform rheological properties of the drilling fluid following its preparation and after exposure (aging), especially in the temperature range from 130xc2x0 C. to more than 200xc2x0 C., which problem is manifested in heightened or fluctuating plastic viscosities, yield points and gel strengths.
It has surprisingly been found that this object is achieved by copolymers which are free from doubly unsaturated ammonium compounds and are composed of structural units derived from AMPS, an open-chain N-vinylamide and a cyclic N-vinylamide. The object is further achieved by copolymers which include certain acrylic derivatives in addition to the said constituents.
The invention therefore provides water-soluble copolymers consisting of the following components:
A 5-95% by weight of bivalent structural units derived from acrylamidopropenylmethylenesulfonic acid or its salts,
B 1-45% by weight of bivalent structural units derived from open-chain N-vinylamides,
C 1-45% by weight of bivalent structural units derived from cyclic N-vinyl-substituted amides,
and if desired
D 0-50% by weight of a further comonomer selected from the group consisting of acrylamide, acrylic acid and acrylonitrile,
the components A to C and, if present, D adding up to 100% by weight.
Component A of the copolymers comprises structural units of the formula 1 
They are derived from AMPS or its salts. X can be hydrogen or Li+, Na+, K+ or NH4+.
Where the copolymer contains only components A, B and C, the proportion of component A is preferably from 60 to 90% by weight. Where the copolymer includes a component D as well, the proportion of component A is preferably from 50 to 90% by weight.
Component B of the copolymer generally comprises structural units of the formula 2 
in which R1 and R2 are H or alkyl radicals. R1 and R2 independently of one another are preferably H or C1-C4 alkyl radicals. In particular, they are independently of one another hydrogen, methyl or ethyl. Particularly preferred structural units of the formula 2 are those where R1 and R2=H, R1=CH3 and R2=H, and R1 and R2=CH3. In a further preferred embodiment, the copolymer contains between 5 and 15% by weight of structural units of the formula 2.
Component C of the copolymer comprises structural units derived from cyclic amides which carry a vinyl radical on the amide nitrogen atom. The cyclic compounds are either aromatic compounds or saturated compounds. In one preferred embodiment of the invention component C comprises structural units of the formula 3 
in which R3 and R4 with the inclusion of the xe2x80x94Nxe2x80x94COxe2x80x94 group form a ring having 5, 6, 7 or 8 ring atoms. Rings having 5, 6 or 7 ring atoms are preferred. R3 and R4 can include heteroatoms, but preferably include only carbon atoms.
In one particularly preferred embodiment, formula 3 represents a structural unit of the formula 3a 
In a further particularly preferred embodiment, formula 3 represents N-vinylcaprolactam.
If component C is derived from an aromatic nitrogen compound, then in one particularly preferred embodiment it comprises a structural unit of the formula 3b 
In a further preferred embodiment of the invention, the copolymer contains from 5 to 10% by weight of structural units of the formula 3.
In one preferred embodiment the copolymer further comprises a component D. This component D comprises structural units of the formula 4 
in which R is xe2x80x94CN, COOX (X=H or monovalent cation) or xe2x80x94CONR52. R5 is hydrogen or C1-C4 alkyl, preferably hydrogen. Where the copolymer includes a component D, its proportion is preferably below 20% by weight, with particular preference 5-10% by weight.
Preferred copolymers have molecular weights of from 50,000 to 5,000,000, in particular from 200,000 to 3,000,000, especially from 500,000 to 1,500,000 units.
The copolymers of the invention are free from diolefinically unsaturated ammonium compounds. The copolymers of the invention are preferably also free from other di- or polyolefinically unsaturated compounds that are able to induce crosslinking as a result of further polymerizations.
The copolymers of the invention can be prepared by the techniques of solution polymerization, bulk polymerization, emulsion polymerization, inverse emulsion polymerization, precipitation polymerization or gel polymerization.
The polymerization is preferably conducted as a solution polymerization in water or as a precipitation polymerization.
When the copolymerization is conducted in a water-miscible organic solvent, the general procedure is to operate under the conditions of precipitation polymerization. In this case the polymer is obtained directly in solid form and can be isolated by distillative removal of the solvent or by filtration with suction followed by drying. Particularly suitable water-miscible organic solvents for conducting the preparation process of the invention are water-soluble alkanols, namely those having 1 to 4 carbon atoms such as methanol, ethanol, propanol, isopropanol, n-, sec- and isobutanol, but preferably tert-butanol.
The water content of the lower alkanols used as solvents in this case should not exceed 6% by weight, since otherwise lumps may be formed during the polymerization. It is preferred to operate with a water content of from 0 to 3% by weight. The amount of solvent to be used depends to a certain extent on the nature of the comonomers that are employed. In general, from 200 to 1000 g of the solvent are used per 100 g of total monomers. When the polymerization is conducted in inverse emulsion, the aqueous monomer solution is emulsified in a known manner in a water-immiscible organic solvent such as cyclohexane, toluene, xylene, heptane or high-boiling petroleum fractions with the addition of from 0.5 to 8% by weight, preferably from 1 to 4% by weight, of known emulsifiers of the W/O type and is polymerized using customary free-radical initiators.
The principle of inverse emulsion polymerization is known from U.S. Pat. No. 3,284,393. With this technique, water-soluble monomers or mixtures thereof are polymerized with heating to form copolymers of high molecular mass by first emulsifying the monomers or aqueous solutions thereof in a water-immiscible organic solvent which forms the continuous phase, with the addition of water-in-oil emulsifiers, and heating this emulsion in the presence of free-radical initiators. The comonomers to be used can be emulsified as such in the water-immiscible organic solvent, or can be used in the form of an aqueous solution containing between 100 and 5% by weight of comonomers and from 0 to 95% by weight of water, the composition of the aqueous solution being a question of the solubility of the comonomers in water and of the intended polymerization temperature. The ratio between water and monomer phase can be varied within wide limits and is generally from 70:30 to 30:70.
In order to emulsify the monomers in the water-immiscible organic solvent to form a water-in-oil emulsion, from 0.1 to 10% by weight, based on the oil phase, of a water-in-oil emulsifier is added to the mixtures. It is preferred to use emulsifiers having a relatively low HLB. The HLB is a measure of the hydrophobicity and hydrophilicity of surfactants and emulsifiers (Griffin, J. Soc. Cosmetic Chemists 1, (1950), 311). Substances having a low HLB, below about 10, are generally good water-in-oil emulsifiers.
The oil phase used can in principle be any inert water-insoluble liquid, i.e., any hydrophobic organic solvent. For the purposes of the present invention use is generally made of hydrocarbons whose boiling point lies within the range from 120 to 350xc2x0 C. These hydrocarbons can be saturated, linear or branched paraffinic hydrocarbons, as predominate in petroleum fractions, which may also include the customary fractions of naphthenic hydrocarbons. However, it is also possible to use aromatic hydrocarbons such as, for example, toluene or xylene, and the mixtures of the abovementioned hydrocarbons, as the oil phase. Preference is given to the use of a mixture of saturated normal and isoparaffinic hydrocarbons containing up to 20% by weight of naphthenes. A detailed description of the technique can be found, for example, in DE-A-1 089 173 and in U.S. Pat. Nos. 3,284,393 and 3,624,019.
Copolymers having molecular weights of more than 1,000,000 are obtained if the polymerization is conducted in aqueous solution by the technique known as gel polymerization. In this case, 15-60% strength by weight solutions of the comonomers are polymerized with known suitable catalysts, without mechanical mixing, utilizing the Trommsdorff-Norrish effect (Bios Final Rep. 363, 22; Macromol. Chem. 1, 169/1947).
Following mechanical comminution using appropriate apparatus, the copolymers of the invention prepared by this route, which are in the form of aqueous gels, can be dissolved directly in water and so used. Alternatively, they can be obtained in solid form after the water has been removed by means of known drying processes, and can be redissolved in water at the time of use.
The polymerization reactions are conducted in the temperature range between xe2x88x9260 and 200xc2x0 C., preferably between 10 and 120xc2x0 C., under either atmospheric or superatmospheric pressure. The polymerization is generally performed under an inert gas atmosphere, preferably under nitrogen.
The polymerization can be initiated using high-energy electromagnetic or corpuscular beams or the customary chemical polymerization initiators, examples being organic peroxides such as benzoyl peroxide, tert-butyl hydroperoxide, methyl ethyl ketone peroxide, cumene hydroperoxide, azo compounds such as azodiisobutyronitrile or 2xe2x80x2-azobis-(2-amidinopropane)dihydrochloride, and inorganic peroxo compounds such as (NH4)2S2O8 or K2S2O8 or H2O2 alone or in combination with reducing agents such as sodium hydrogen sulfite and iron(II) sulfate or redox systems containing as reducing component an aliphatic or aromatic sulfinic acid such as benzenesulfinic acid and toluenesulfinic acid or derivatives of these acids, such as, for example, Mannich adducts of sulfinic acid, aldehydes and amino compounds, as are described in DE-C-13 01 566. From 0.03 to 2 g of the polymerization initiator are generally used per 100 g of total monomers.
Small amounts of what are known as moderators may be added to the polymerization mixtures: these moderators harmonize the progress of the reaction by flattening the reaction rate/time plot. They therefore lead to an improvement in the reproducibility of the reaction and so enable the preparation of uniform products having a narrow molar mass distribution and high chain length. Examples of suitable moderators of this type are nitrilotrispropionylamide or monoalkylamines, dialkylamines or trialkylamines, such as dibutylamine, for example. Such moderators may also be used with advantage in the preparation of the copolymers of the invention. Furthermore, regulators can be added to the polymerization mixtures, these regulators adjusting the molecular weight of the resultant polymers by means of targeted chain termination. Known regulators which can be used are, for example, alcohols such as methanol, ethanol, propanol, isopropanol, n-butanol and amyl alcohols, alkyl mercaptans such as dodecyl mercaptan and tert-dodecyl mercaptan, isooctyl thioglycolate and certain halogen compounds such as, for example, carbon tetrachloride, chloroform and methylene chloride. The copolymers of the invention are outstandingly suitable as aids for drilling fluids. They display a very good protective colloid effect both at high temperatures and at high electrolyte concentrations, and in terms of electrolyte stability and aging stability correspond to the prior art. In terms of the action in reducing pressurized water and of the rheological behavior following preparation and aging over the entire temperature range from 130 to more than 200xc2x0 C., they are considerably superior to the copolymers known to date from U.S. Pat. Nos. 3,629,101, 4,048,077 and 4,309,523.
To formulate aqueous drilling fluids the copolymers of the invention are used in concentrations of from 0.5 to 40 kg/m3, preferably from 3 to 30 kg/m3. In order to increase viscosity and seal off formations through which drilling has taken place, the aqueous drilling fluids contain predominantly bentonites. Barite, chalk and iron oxides are used to raise the density of the drilling muds.
Bentonite, barite, chalk and iron oxide can be added alone or in any of a wide variety of mixing proportions to the drilling fluids. The limiting factor on the upward side are the rheological properties of the drilling muds.
The preparation and use of the polymers of the invention are illustrated with the following examples.